Search results for "Activation energy"
showing 10 items of 238 documents
Numerical Studies of the Diffusion Processes and First Step Oxidation in Nickel-Oxygen Systems by Variable Charge Molecular Dynamics
2010
Variable charge molecular dynamic simulations have been performed to study the diffusion mechanisms of oxygen atoms (O) in nickel (Ni) in the temperature range 950-1600 K and the very first steps of oxidation of monocrystalline nickel surfaces at 300 K and 950 K. The oxygen diffusivity can be well described by an Arrhenius law over the temperature range considered. The oxygen diffusion coefficient has been analysed and values of Ea = 1.99 eV for the activation energy and D0 = 39 cm2.s-1 for the pre-exponential factor were obtained. The first steps growth of the oxide layer show that after the dissociative chemisorption of the oxygen molecules on nickel surface, the oxidation leads to an isl…
Modeling polyethylene with the bond fluctuation model
1997
This work presents an application of recently developed ideas about how to map real polymer systems onto abstract models. In our case the abstract model is the bond fluctuation model with a Monte Carlo dynamics. We study the temperature dependence of chain dimensions and of the self-diffusion behavior in the melt from high temperatures down to 200 K. The chain conformations are equilibrated over the whole temperature range, which is possible for the abstract type of model we use. The size of the chains as measured by the characteristic ratio is within 25% of experimental data. The simulated values of the chain self-diffusion coefficient have to be matched to experimental information at one …
Temperature dependance of the generation and decay of E’ centers induced in silica by 4.7eV laser radiation
2009
We report a study of the generation of silicon dangling bonds (E' centers) induced in fused silica by 4.7 eV laser irradiation in the 10 200 K the induced defects undergo a post-irradiation decay due to their reaction with mobile H(2). The interplay between generation and annealing gives rise to a bell-shaped temperature dependence of the concentration of induced E' centers, peaking at 250 K
Kinetischer nachweis zweier arten von ionenpaaren bei der anionischen polymerisation von styrol in tetrahydropyran
1967
Die durch Na-Naphthalin angeregte Polymerisation des Styrols in THP wurde im Temperaturbereich von -40 bis +50°C kinctisch verfolgt. Die Geschwindigkeitskonstante kw(±) der uber das lonenpaar erfolgenden Polymerisation wurde gemessen, indem die elektrolytische Dissoziation durch Zusatz von Tetraphenylbornatrium unterdruckt wurde. Oberhalb von 20°C ergibt sich bei Auftragung nach ARRHENIUS eine Gerade, aus welcher Aktivierungsenergie Ec und Frequenzfaktor Ac des Kontaktionenpaares zu berechnen sind. Diese Parameter stimmen in guter Naherung mit den E- und A- Werten uberein, die in sehr schwach polaren Losungsmitteln fur die anionische Polymerisation erhalten werden. Unterhalb von +20°C weich…
1981
The anionic polymerization of tert-butyl methacrylate (TBMA) in tetrahydrofuran, using Na+ and Cs+ as counterions proceeds without side reactions even at room temperature. The resulting molecular weight distributions are nearly monodisperse (Mw/Mn ⩽ 1,01). The rate constants for the propagation of ion pairs were measured in the range from + 15 to −100°C. The Arrhenius plots are linear, but different for the two counterions, resulting in the following numerical values for the frequency exponent A and the activation energy Ea: A = 8,5 and Ea = 7,2 kcal/mol = 30 kJ/mol for Na+; A = 9,5 and Ea = 5,6 kcal/mol = 23 kJ/mol for Cs+. The difference between the counterions, which is in contrast to th…
A combined experimental and theoretical study of the thermal cycloaddition of aryl azides with activated alkenes.
2011
International audience; Reactions were performed from aryl azides on the one hand, and activated alkenes coming from β-dicarbonyl compounds or malonodinitrile on the other hand, either with recourse to conventional heating or to microwave activation, to afford 1-aryl-1H-1,2,3-triazoles. The mechanism and the regioselectivity of the reactions involving β-dicarbonyl compounds have been theoretically studied using DFT methods at the B3LYP/6-31G* level: they are domino processes comprising a tautomeric equilibrium of the β-dicarbonyl compounds with their enol forms, a 1,3-dipolar cycloaddition of the enol forms with the aryl azides (high activation energy), and a dehydration process (lower acti…
Chemistry inside molecular containers in the gas phase.
2013
Inner-phase chemical reactions of guest molecules encapsulated in a macromolecular cavity give fundamental insight into the relative stabilization of transition states by the surrounding walls of the host, thereby modelling the situation of substrates in enzymatic binding pockets. Although in solution several examples of inner-phase reactions are known, the use of cucurbiturils as macrocyclic hosts and bicyclic azoalkanes as guests has now enabled a systematic mass spectrometric investigation of inner-phase reactions in the gas phase, where typically the supply of thermal energy results in dissociation of the supramolecular host-guest assembly. The results reveal a sensitive interplay in wh…
Influence of chitin nanocrystals on the dielectric behaviour and conductivity of chitosan-based bionanocomposites
2018
[EN] A series of bionanocomposite films based on chitosan, reinforced with chitin nanocrystals, were developed, and assessed in terms of dielectric behaviour and conductivity by using an experimental methodology that allows avoiding the conductivity contribution and the exclusion of contact and interfacial polarization effects. The dielectric relaxations at low and high frequency and temperatures were modeled by Havriliak-Negami functions. Below the glass transition temperature (Tg), the gamma and beta relaxations were observed, which were related to intramolecular and non-cooperative segmental movements. At higher temperatures, an intermolecular and cooperative macromolecular movement, rel…
ChemInform Abstract: Inorganic Materials Acting as Heterogeneous Photocatalysts and Catalysts in the Same Reactions
2016
General considerations on the differences and similarities between heterogeneous photocatalysis and thermal catalysis are presented. Some research papers are reviewed where a reaction has been carried out in the presence of an inorganic material used both as catalyst and photocatalyst. The existing literature often compares catalytic reactions undertaken with the contemporaneous presence of radiation, showing only that photocatalytic reactions can occur under milder experimental conditions and at much lower temperatures. Nevertheless, differences in mechanistic aspects, conversions and selectivities between catalytic and photocatalytic reactions should also be highlighted. These are due to …
Quantum chemical calculations of the electron center diffusion in MgO crystals
1996
Large-scale quantum chemical simulations of the diffusion hops of empty cation and anion vacancies, as well as F + and F centers in MgO crystals have been done. The atomic configurations for 224-site cluster and charge density distribution are analyzed for the equilibrium and saddle-point configurations during the defect hops. The relevant activation energy for diffusion increases monotonically in the series V a → F + → F center.